2-Nitro-5(substituted-phenoxy) benzoyl derivatives as herbicides

ABSTRACT

There is provided a new class of derivatives of 2-nitro-5-(substituted-phenoxy) benzoyl compounds that have pre- and post-emergence herbicidal activity. The derivatives include certain substituted phenyl esters, phenyl thioesters; heterocyclic esters; substituted alkyl and alkylthio esters; carbonates and thiocarbonates; benzoyl phosphonates; substituted alkanones and substituted amides.

CROSS-REFERENCES TO RELATED APPLICATIONS

This is a division of application Ser. No. 282,316 filed July 10, 1981, which is a continuation-in-part application No. Ser. No. 117,732 filed Feb. 1, 1980, now abandoned.

Applicant Theissen herein has been granted a series of patents relating to 2-nitro-5-(substituted-phenoxy) benzoic acid derivatives including the salt, alkyl and cycloalkyl esters, alkylthio esters, phenyl ester, alkyl and dialkyl amido and benzoyl chloride forms. Illustrative of those patents are U.S. Pat. Nos. 3,652,645; 3,784,635; 3,873,302; 3,983,168 and 3,907,866.

BRIEF SUMMARY OF THE INVENTION

This invention provides certain herbicidal compounds falling within the general formula: ##STR1## wherein X₁ is halogen, X₂ is selected from halogen and hydrogen, and Z is a polyhalo₁₋₉ alkyl₁₋₄ group such as CF₃, CHF₂, C₄ F₉, CF₂ CH₂ CH₃ and CH₂ Cl. Preferably, X₁ is chloro, Z is CF₃ and X₂ is hydrogen. QA in the formula includes certain groups more fully described below.

DETAILED DESCRIPTION

The specific 2-nitro-5-(substituted-phenoxy) benzoyl compounds are described below. One method for preparing these compounds is the use of the Ullman ether synthesis reaction between the alkali metal (e.g., Na, K) salt of a suitable substituted phenol, e.g., m-hydroxy benzoic acid or m-cresol with an active halogen-substituted aromatic, e.g., 3,4-dichlorobenzotrifluoride. The intermediate obtained may be nitrated and subsequently derivatized by known procedures to the desired benzoyl compound. Where m-cresol is used as a starting material, the product obtained can be oxidized and subsequently nitrated before the aforementioned derivatization.

A. Substituted phenyl esters, phenylthio ester, substituted phenylthio esters

Illustrative compounds of this class are those of the formula: ##STR2## where

Q is O or S,

n is an integer from 1 to 5, and

X is selected from NO₂ ; lower alkyl of C₁₋₄ ; halogen; phenyl; COOR where R is lower alkyl of C₁₋₄, H or a cation selected from alkali metals, alkaline earth metals, ammonium and lower alkyl and di-lower alkyl ammonium; CN; lower alkyl thio of C₁₋₄ ; lower alkoxy of C₁₋₄ ; trifluoromethyl; and combinations thereof. X can be hydrogen when Q is sulfur.

Compound 1

Preparation of 2,4-dinitro-6-sec-butylphenyl 5-[-2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate.

To a stirred solution of 2,4-dinitro-6-sec-butylphenol (3.60 g, 0.015 mole) and 5-[-2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoyl chloride (5.68 g, 0.015 mole) in toluene (25 ml) was added triethylamine (1.50 g, 0.015 mole). The temperature exothermed to 45° C. and there was an immediate precipitation of triethylamine hydrochloride. The reaction was stirred and heated to 110° F. for 15 hours. The precipitate was filtered from the cooled solution, washed and dried to give triethylamine hydrochloride (1.8 g). The toluene solution was washed with 10% sodium hydroxide (3×25 ml). The toluene was then stripped off on a rotary evaporator to give 5.5 g (62%) of a crude brown oil which slowly crystallized. Recrystallization from methanol gave 2.1 g of an off white solid, mp. 109°-110° C.

I.R. (nujol): C═O, 1765 cm⁻¹

NMR (D6 Acetone): triplet 0.9 ppm (3H, J=7.0 Hz): doublet 1.37 ppm (3H, J=7.0 Hz): multiplet 1.82 ppm (2H); multiplet 3.35 ppm (1H); multiplet 7.5-8.2 (5H); doublet 8.45 ppm (1H, J=9.0 Hz); doublet 8.82 ppm (1H, J=2.4 Hz); doublet 9.02 ppm (1H, J=2.4 Hz).

In a similar manner the following compounds were prepared as defined according to Formula II:

    ______________________________________                                                  Q          Phenyl Substitution                                        Compound (O or S)   X.sub.n        m.p., °C.                            ______________________________________                                         2        O          2-NO.sub.2     137-9                                       3        O          3-NO.sub.2     93.5                                        4        O          4-NO.sub.2     115-7                                       5        O          5-CH.sub.3 --2NO.sub.2                                                                        88-90                                       6        O          2-Cl--4NO.sub.2                                                                               99-101                                      7        O          4-Cl           135-7                                       8        O          4-Cl--2-CH.sub.3                                                                              121-2                                       9        O          2-Cl--4-CH.sub.3                                                                              105-7                                       10       O          2-Cl--4-phenyl 128-30                                      11       O          2,4-(Cl).sub.2 144-7                                       12       O          4-COOCH.sub.3  103-6                                       13       O          4-CN           103-5                                       14       O          4-SCH.sub.3    94-5                                        15       O          3-OCH.sub.3    95-7                                        16       O          4-OCH.sub.3    128-9                                       17       O          3-CF.sub.3     oil                                         18       O          4-COONa        215-20                                      19       O          4-COOH         191-8                                       20       S          H              oil                                         21       S          4-Cl           128-30                                      22       S          4-CH.sub.3     90-3                                        23       S          4-OCH.sub.3    oil                                         24       S          3,4-(Cl).sub.2 oil                                         ______________________________________                                    

Other compounds of this class include:

    ______________________________________                                          ##STR3##       Compound                                                       ______________________________________                                          ##STR4##      2,6-diethylphenyl 5-[2-chloro-4- (trifluoromethyl)                             phenyoxy]-2- nitrobenzoate                                       ##STR5##      S[2-carboxyphenyl) 5-[2-chloro- 4-(trifluoromethyl)                            phenoxy]-2- nitrobenzenecarbothioate                             ##STR6##      4-cyano-2,6-dibromophenyl 5-[2-chloro-4-(trifluoromethyl)                      phenoxy]-2-nitrobenzoate                                         ##STR7##      3,6-dichloro-2-methoxycarbonyl- phenyl 5-[2-chloro-4-                          (trifluoromethyl) phenoxy]-2- nitrobenzoate                      ##STR8##      (2,6-di-6-butyl) phenyl 5-[2- chloro-4-(trifluoromethyl)                       phenoxy]-2-nitrobenzoate                                         ##STR9##      pentachlorophenyl 5-[2-chloro- 4-(trifluoromethyl)                             phenoxy]-2- nitrobenzoate                                       ______________________________________                                    

B. Heterocyclic Esters

Illustrative compounds of this class are those of the formula: ##STR10## where Q is O or S and Het is a substituted or unsubstituted heterocyclic ring of 5 to 7 members comprising carbon in combination with one or more of sulfur, oxygen and nitrogen where a carbon atom on the ring is bound directly to Q.

Compound 25

Preparation of 3-pyridyl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate: To a stirred solution of 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoyl chloride (3.79 g, 0.01 mole) and triethyl amine (1.01 g, 0.01 mole) in toluene (50 ml) was added 3-hydroxypyridine (0.95 g, 0.01 mole). The temperature exothermed to 33° C. and there was an immediate precipitate. The reaction was then refluxed for 24 hours, cooled to room temperature and the triethylamine hydrochloride precipitate collected by filtration. The toluene solution was washed with dilute sodium hydroxide solution and then with saturated sodium chloride solution. After drying and evaporation of the solvent there was obtained 3.1 g of brown oil which solidified. This was triturated with hexane and the solid filtered and dried to give a tan product, m.p. 65°-68° C.

I.R. (nujol): C═O, 1765 cm⁻¹

NMR(D₆ -acetone): complex multiplet 7.2-8.1 ppm (7H); doublet 8.50 ppm (1H, J=4.5 Hz); multiplet 8.75 ppm (2H).

Compound 26

This compound is defined in accordance with Formula III as "Q" is O and "Het" is ##STR11## The compound was prepared by the procedure shown for Compound 25. Compound 26 has an m.p. of 153°-161° C.

Other compounds of this class include:

    ______________________________________                                         QHet            Compound Name                                                  ______________________________________                                          ##STR12##      3-(1,2,5 thiadiazoloyl)-5-[2- chloro-4-trifluoromethyl)                        phenoxy]-2-nitrobenzoate                                        ##STR13##      1,2-dihydro-1,6-dimethyl-2-oxo 4-pyridinyl 5-[2-chloro-4-                      trifluoromethyl) phenoxy]-2- nitrobenzoate                      ##STR14##      6(2,3-dihydro-3-oxo-pyridazinyl) 5-[2-chloro-4-(trifluorom                     ethyl) phenoxy]-2-nitrobenzoate                                 ##STR15##      2-chloro-6-pyridinyl 5-[2-chloro- 4-(trifluoromethyl)                          phenoxy]-2- nitrobenzoate                                       ##STR16##      s-(2,6-dichloro-4-s-triazinyl) 5-[2-chloro-4-(trifluoromet                     hyl) phenoxy]-2-nitrobenzoate                                   ##STR17##       S(2-methyl 1,3,4,-thiadiazol- 5-yl) 5-[2-chloro-4-trifluo                     ro- methyl) phenoxy]-2-nitrobenzene- carbothioate               ##STR18##      S(2-pyridinyl) 5-[-2-chloro-4- (trifluoromethyl)                               phenoxy]-2- nitrobenzenecarbothioate Noxide                     ##STR19##      S[4-methyl-3-thioxo-3H1,2- dithiol-5-yl] 5-[2-chloro-4-                        (trifluoromethyl) phenoxy]-2- nitrobenzene-carbothioate         ##STR20##      S[3,5-bis-(diethylamino)-s-tri- azinyl] 5-[2-chloro-4-(tri                     fluoro- methyl) phenoxy]-2-nitrobenzene- carbothioate          ______________________________________                                    

Substituted C₁₋₄ Alkyl Esters

Illustrative compounds of this class are those of the formula: ##STR21## wherein the substituents on the straight or branched C₁₋₄ alkyl group are selected from cyano; phenyl; ##STR22## where n is 1 to 5 and X is selected from NO₂, lower alkyl or C₁₋₄, halogen, phenyl, CN, lower alkyl thio of C₁₋₄, lower alkoxy of C₁₋₄, trifluoromethyl and combinations thereof; ##STR23## phenoxy; nitro; SR₁ ; SOR₁ ; SO₂ R₁ ; where R₁ is an alkyl of 1 to 3 carbons and R₂ is an alkyl or alkenyl of up to 3 carbons and wherein one or more of said substituents can be attached to any one or more of the carbons on said straight or branched C₁₋₄ alkyl group.

The compounds of this class may be prepared by the methods shown above or alternatively by displacement of an active halogen (e.g., Haloalkyl X) with the salt of an acid (e.g., ##STR24##

The following substituted C₁₋₄ alkyl esters as defined by Formula IV were prepared:

    ______________________________________                                         Compound                                                                               Substituted Alkyl Group                                                                             m.p. °C.                                   ______________________________________                                         27      C(CH.sub.3).sub.2 CN oil                                               28      CH(CH.sub.3)CN       oil                                               29      CH.sub.2 COCH.sub.3  83-5                                              30                                                                                      ##STR25##           oil                                                 31                                                                                    ##STR26##           oil                                                 32                                                                                    ##STR27##           oil                                                 33                                                                                    ##STR28##           oil                                                 34    CH.sub.2CH.sub.2CN   oil                                               35                                                                               36                                                                                    ##STR29##           86-8                                                37                                                                                    ##STR30##           112-3                                               38    CH.sub.2 C(CH.sub.3).sub.2NO.sub.2                                                                  oily semisolid                                    39      CH.sub.2CH.sub.2SCH.sub.3                                                                           oil                                               40      CH.sub.2CH.sub.2SO.sub.2 CH.sub.3                                                                   97-9                                              ______________________________________                                    

Other compounds of this class include:

    ______________________________________                                         Substituted alkyl                                                                             Compound Name                                                   ______________________________________                                         CH.sub.2SCH.sub.2 CH.sub.3                                                                    (ethylthio)methyl 5-[2-chloro-4-                                               (trifluoromethyl) phenoxy]-2-                                                  nitro-benzoate                                                   ##STR31##     (ethylsulfinyl)methyl 5-[2-chloro- 4-(trifluoromethyl)                         phenoxy]-2- nitro-benzoate                                       ##STR32##     (ethylsulfinyl)methyl 5-[2-chloro- 4-(trifluoromethyl)                         phenoxy]- 2-nitrobenzoate                                        ##STR33##     1-acetylethyl 5-[2-chloro-4-tri- fluoromethyl)                                 phenoxy]-2-nitro- benzoate                                       ##STR34##     3-acetylpropyl 5-[2-chloro-4-(trifluoromethyl) phenoxy]-2-n                    itrobenzoate                                                     ##STR35##     2-(methylsulfinyl) ethyl 5-[2- chloro-4-(trifluoromethyl)                      phenoxy]-2-nitrobenzoate                                         ##STR36##     (3-fluorophenyl) methyl 5-[2-chloro-4-(trifluoromethyl)                        phenoxy]-2-nitrobenzoate                                        ______________________________________                                    

D. Carbonates and Thiocarbonates

Illustrative compounds of this class are those of the formula: ##STR37## where Q is O or S and Y is a straight or branched alkoxy or alkylthio of 1 to 6 carbons, a dialkylamino of 2 to 6 carbons, or a heterocyclic amine such as morpholine.

Compound 41

Preparation of S[(ethylthio)carbonyl]5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate.

To a stirred solution of 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid (3.0 g, 0.0083 mole) in ether (15 ml) was added triethylamine (0.84 g, 0.0083 mole). A precipitate formed. The reaction was cooled to 4° C. and a solution of ethylchlorothioformate (1.03 g, 0.0083 mole) in ether was added dropwise. Cooling was maintained during initial exotherm. The reaction was then stirred at room temperature for twenty hours. The precipitate of triethyl amine hydrochloride was filtered. The ether was washed consecutively with 10% hydrochloric acid solution, 5% sodium hydroxide solution and water. The dried solution was evaporated to give 3.04 g of a yellow oil.

I.R. (neat): C═O, 1675 and 1800 cm⁻¹

NMR (CDCl₃): triplet 1.37 ppm (3H, J=7.0 Hz); quartet 3.12 ppm (2H, J=7.0 Hz); complex multiplet 7.0-8.0 ppm (5H); doublet 8.15 ppm (1H, J=9.6 Hz).

In a similar manner, the following compounds, as defined in accordance with Formula V, were prepared:

    ______________________________________                                         Compound Q       Y             m.p. °C.                                 ______________________________________                                         42       O       OCH.sub.3     oil                                             43       O       OCH.sub.2 CH.sub.3                                                                           oil                                             44       O       OCH.sub.2 CH.sub.2 CH.sub.3                                                                  oily semi-solid                                 45       O       OCH(CH.sub.3).sub.2                                                                          oily semi-solid                                 46       O       OCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                         oil                                             47       O       OCH.sub.2 CH(CH.sub.3).sub.2                                                                 oil                                             48       S       OCH.sub.3     oil                                             49       S                                                                                       ##STR38##    137-8°                                   ______________________________________                                    

S[(propylthio)thionocarbonyl]5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzenecarbothioate is a further illustrative compound of this class wherein Q is S and Y is --SC₃ H₇.

Benzoyl Phosphonates

Illustrative compounds of this class are those of the formula: ##STR39## where R₃ is straight or branched alkyl of 1 to 6 carbons.

Compound 50

Preparation of 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoyl-phosphonic acid, diisopropyl ester.

To a stirred solution of 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoyl chloride (3.8 g, 0.01 mole) in ether (100 ml) was added triisopropyl phosphite (2.1 g, 0.01 mole). The reaction was refluxed for one hour and the disappearance of phosphite monitored by v.p.c.. The ether was stripped off and the resulting oil placed under vacuum (1.0 mm) at 40° C. for two hours. The resulting amber liquid amounted to 5.2 g.

I.R. (neat): C═O, 1692 and 1730 cm⁻¹

NMR (CDCl₃): doublet 1.29 ppm (3H, J=6.0 Hz); doublet 1.37 ppm (3H, J=6.0 Hz); multiplet 4.88 ppm (1H); complex multiplet 6.9-8.0 ppm (5H); broad doublet 8.37 ppm (1H, J=9.0 Hz).

In a similar manner, the following compound was prepared as an additional example of a benzoyl phosphonate.

Compound 51

5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoy-phosphonic acid diethyl ester was prepared and was an oil.

F. Substituted Alkanone Compounds

Illustrative compounds of this class are those of the formula: ##STR40## where A is an alkyl of 1-3 carbons or hydrogen.

Compound 52

Preparation of 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrophenyl ethanone (A is --CH₃).

A stirred solution of 3-[2-chloro-4-(trifluromethyl)phenoxy]phenyl ethanone (15.7 g, 0.05 mole) in dichloroethane (40 ml) was cooled to 0.5° C. Nitric acid (95%) (4.95 g, 0.075 mole) was added, followed by the dropwise addition of 95% sulfuric acid (12.3 g, 0.125 mole) while maintaining the temperature below 5°-10° C. Allowed reaction to warm to room temperature. The progress of the reaction was monitored by v.p.c. The reaction solution was poured onto ice water and the organic solution separated, washed with water and dried. The solvent was evaporated to give 16 g of a brown oil, which was extracted with hot heptane. Upon cooling, the heptane solution furnished an oil fraction which solidified to give 8.8 g of a brown solid, m.p. 58°-60° C.

I.R. (nujol mull): C═O, 1710 cm⁻¹ ; NO₂, 1530 and 1315 cm⁻¹.

Compound 53

5-[2-chloro-4-trifluoromethyl)phenoxy]-2-nitrobenzaldehyde ("A" is hydrogen in Formula VII) was prepared. It had a melting point of 99°-100° C.

G. Amides

Illustrative compounds of this class include those of the formula: ##STR41## wherein

R₄ is selected from hydrogen and straight or branched chain alkyl of 1-4 carbon:

R₅ is selected from: phenyl; ##STR42## where n is 1 to 5 and X is selected from NO₂, lower alkyl of C₁₋₄, halogen, phenyl, COOR where R is lower alkyl of C₁₋₄ or H or a cation, CN, lower alkyl thio of C₁₋₄, lower alkoxy of C₁₋₄, trifluoromethyl and combinations thereof; heterocyclicalkyl and heterocyclic, heterocyclics of a 5 to 7 member ring comprising carbon in combination with one or more of sulfur, oxygen and nitrogen; hydroxyl; alkoxy of 1-3 carbons; --R₆ CO₂ R₆, where R₆ is an alkyl or alkenyl of up to 3 carbons; --R₆ CONH₂ ; R₆ CON(R₂)₂ ; alkoxyalkyl where the alkoxy and alkyl may each contain a straight or branched C₁₋₃ alkyl chain; or

where R₄ and R₅ together form a heterocyclic ring as hereinabove defined.

Compound 54

Preparation of N-phenyl 5-[2-chloro-4-(trifluoromethyl)phenoxyl]-2-nitrobenzamide.

To a stirred solution of 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoyl chloride (5.68 g, 0.015 mole) in toluene (35 ml) was added aniline (2.8 g, 0.30 mole). The temperature immediately rose to 45° C. The reaction was then heated to reflux for twelve hours. The cooled reaction was poured into dilute hydrochloric acid solution. The residual solids were filtered, washed with warm water and dried to give 4.1 g of a gray solid m.p. 190°-4° C. Recrystallization from methanol gave 3.8 g, m.p. 191°-4° C.

I.R. (nujol): C═O, 1660 cm⁻¹

NMR (D₆ -Acetone): complex multiplet 7.0-8.1 ppm (10H); doublet 8.32 ppm (1H, J=9.0 Hz); broad singlet 9.95 ppm (1H).

In a similar manner, the following compounds were prepared:

    ______________________________________                                         Compound R.sub.4   R.sub.5         m.p. °C./oil                         ______________________________________                                         55       H                                                                                         ##STR43##      145-8                                         56     H                                                                                         ##STR44##      179-81                                        57     H                                                                                         ##STR45##      155-8                                         58     H                                                                                         ##STR46##      169-71                                        59     H                                                                                         ##STR47##      185-7                                         60     CH(CH.sub.3).sub.2                                                                        ##STR48##      144-6                                         61     H                                                                                         ##STR49##      140-1                                         62     H         OH              oil                                           63     H         OCH.sub.3       171-4                                         64     CH.sub.3  OH              oil                                           65     CH.sub.3  OCH.sub.3       oil                                           66     H         CH.sub.2 COOC.sub.2 H.sub.5                                                                    136-7                                         67     H                                                                                         ##STR50##      oil                                         68       H                                                                                         ##STR51##      160-3                                         69     H         CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                             86-8                                          70     H         CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                           102-4                                         71     H                                                                                         ##STR52##      158-60                                      ______________________________________                                         Compound R.sub.4 and R.sub.5   m.p. °C./oil                             ______________________________________                                         72                                                                                       ##STR53##            107-8                                             73                                                                                     ##STR54##            128-32                                            74                                                                                     ##STR55##            124-6                                             75                                                                                     ##STR56##            169-72                                            76                                                                                     ##STR57##            oil                                               77                                                                                     ##STR58##            125-8                                           ______________________________________                                          ##STR59##        Compound Name                                                ______________________________________                                          ##STR60##       N[2-(5-t-butyl-1,3,4 thiadia- zolyl)]5-[2-chloro-4-(trifl                      uoro- methyl)phenoxy]-2-nitro- benzamide                       ##STR61##       5-[2 chloro-4-(trifluoromethyl) phenoxy]-2-nitrobenzoyl                        2,5-dioxopyrolidine                                            ##STR62##       N[2-(4,6,6-trimethyl-1,3- thiazinyl)]5-[2-chloro-4-(tri-                       luoromethyl)phenoxy]-2-nitro benzamide                         ##STR63##       N(carboxymethyl)5-[2- chloro-4-(trifluoro- methyl)phenoxy                      ]-2-nitro benzamide                                            ##STR64##       Ncarboxymethyl-Nmethyl 5-[2-chloro-4-(tri- fluoromethyl)p                      henoxy]-2- nitrobenzamide                                      ##STR65##       N(2,5-dichloro-3-methoxy- carbonyl)phenyl 5-[2-chloro-4-                       trifluoromethyl)phenoxy]- 2-nitrobenzamide                     ##STR66##       N[4-[6-(1,1-dimethylethyl)-3- methylthio-1,2,4-triazin-5(                      4H) onyl]]5-[2-chloro-4-(trifluoro- methyl)phenoxy]-2-                         nitrobenzamide                                                 ##STR67##       N(3,4-dimethyl-2,6- dinitrophenyl)- N(1-methylethyl)                           5-[2-chloro-4-(tri- fluoromethyl)phenoxy]- 2-nitrobenzami                      de                                                             ##STR68##       N[2,6-dinitro-4-(tri- fluoromethyl)phenyl]- Nethyl                             5-[2-chloro-4- (trifluoromethyl)phenoxy]-2- nitrobenzamid                      e                                                             ______________________________________                                    

H. Other Benzoyl Compounds

The following 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitro-benzoyl compounds do not readily fall within the defined classes A-G above and are therefore listed below:

Compund 78

2-chloro-cyclohexyl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate (oil).

Compound 79 ##STR69## [m.p. 134°-6° C.] Compound 80

S-(4-chloro-benzyl) 5-[(2-chloro-4-trifluoromethyl)phenoxy]-2-nitro-benzene carbothioate. [oil]

Compound 81 ##STR70##

Additional illustrative compounds are listed below according to the structural formula:

    __________________________________________________________________________      ##STR71##                                                                     QA                  Compound Name                                              __________________________________________________________________________      ##STR72##          4-(2,4-difluorophenyl)-2-(methoxy- carbonyl)phenyl                             5-[2-chloro-4-(trifluoromethyl) phenoxy]-2-nitrobenzoa                         te                                                          ##STR73##          4-(ethoxycarbonylethyl)-2-hydroxy- phenyl 5-[2                                 chloro-4(tri- fluoromethyl)phenoxy]-2- nitrobenzoate        ##STR74##          3,5-dinitro-4-dipropylaminophenyl 5-[2-chloro-4-(trifl                         uoromethyl) phenoxy]-2-nitrobenzoate                        ##STR75##          2,6-bis(hydroxymethyl)-4-methyl- phenyl                                        5-[2-chloro-4-(trifluoro- methyl)phenoxy]-2-nitrobenzo                         ate                                                         ##STR76##          3-(1,2,5,6-diisopropylidene-D-  glucosyl)5-[2-chloro-4                         -(tri- fluoromethyl)phenoxy]-2-nitro- benzoate              ##STR77##          2-chloro-9-(methoxycarbonyl) 9Hfluoran-9-yl                                    5-[2-chloro-4- (trifluoromethyl)phenyl]-2- nitrobenzoa                         te                                                          ##STR78##          α-benzoyl (phenylmethyl)5-[2- chloro-4-(trifluor                         omethyl)phenoxy]- 2-nitrobenzoate                           ##STR79##          2-(acetylamino)ethyl 5-[2-chloro- 4-(trifluoromethyl)p                         henoxy]-2- nitrobenzoate                                    ##STR80##          2-(2-methylpropanoyl- amino)ethyl 5-[ 2-chloro-4-                              (trifluoromethyl)phenoxy]- 2-nitrobenzoate                  ##STR81##          [3-(dimethylamino)-2-methyl propionyloxy]ethyl 5-[2-                           chloro-4-(trifluoromethyl) phenoxy]-2-nitrobenzoate         ##STR82##          2-(2-methylpropenoyloxy)-2- methylethyl                                        5-[2-chloro-4-(tri- fluoromethyl)phenoxy]-2-nitro-                             benzoate                                                    ##STR83##          (1-cyano-1 methyl)ethoxymethyl 5-[2-chloro-4-(trifluor                         omethyl) phenoxy]-2-nitrobenzoate                           ##STR84##          (ethoxycarbonyl)(acetyl)methyl 5-[2-chloro-4-(trifluor                         omethyl) phenoxy]-2-nitrobenzoate                           ##STR85##          diethoxyphosphonylmethyl 5-[2- chloro-4-(trifluorometh                         yl)phenoxy]- 2-nitrobenzoate                                ##STR86##          dimethoxyphosphonylethyl 5-[2- chloro-4-(trifluorometh                         yl)phenoxy]- nitrobenzoate                                  ##STR87##          dimethoxyphosphonylethoxy ethyl 5-[2-chloro-4-(tri-                            fluoromethyl) phenoxy]-2-nitrobenzoate                      ##STR88##          2-(chloroacetyl)ethyl 5-[2-chloro- 4-(trifluoromethyl)                         phenoxy]-2- nitrobenzoate                                    OCHF.sub.2        difluoromethyl 5-[2-chloro-                                                    4-(trifluoromethyl)phenoxy]-2-                                                 nitrobenzoate                                               ##STR89##          propenoylaminomethyl 5-[2-chloro- 4-(trifluoromethyl)p                         henoxy]- 2-nitrobenzoate                                    ##STR90##          cyano(ethoxycarbonyl)methyl 5-[2- chloro-4-(trifluorom                         ethyl)phenoxy]- nitrobenzoate                               ##STR91##          4-(3-chlorophenylcarbamoyloxy) butyn-2-yl                                      5-[2-chloro-4- (trifluoromethyl)phenoxy]-2- nitrobenzo                         ate                                                         ##STR92##          N(Chloroacetyl)-N(2,6-diethyl- phenylamino)methyl                              5-[2-chloro-4-(trifluoromethyl) phenoxy]-2-nitrobenzoa                         te                                                           OCH.sub.2 CHCHCN  3-cyanopropen-2-yl                                                             5-[2-chloro-4-(trifluoromethyl)                                                phenoxy]-2-nitrobenzoate                                   SCN                 5-[2-chloro-4-(trifluoromethyl)                                                phenoxy]-2-nitrobenzoic acid                                                   anhydride with thiocyanic acid                              ##STR93##          S(phenylsulfonylaminoethyl)5-[2- chloro-4-(trifluorome                         thyl)phenoxy] 2-nitrobenzenecarbothioate                    ##STR94##          S(2,3-Dihydroxypropyl)5-[2-chloro- 4-(trifluoromethyl)                         phenoxy]-2- nitrobenzenecarbothioate                         SCH.sub.2 COOC.sub.2 H.sub.5                                                                     S(ethoxycarbonylmethyl)5-[2-                                                   chloro-4-(trifluoromethyl)                                                     phenoxy]-2-nitrobenzenecarbothioate                          SCH.sub.2 COOH    S(carboxymethyl)5-[2-chloro-4-                                                 (trifluoromethyl)phenoxy]-2-                                                   nitrobenzenecarbothioate                                    ##STR95##          S[(3-fluorophenyl)methyl]5-[2- chloro-4-(trifluorometh                         yl)phenoxy]- 2-nitrobenzenecarbothioate                     ##STR96##          S[(ethylthiocarbonyl)methyl] 5-[2-chloro-4-(trifluorom                         ethyl) phenoxy]-2-nitrobenzene- carbothioate                ##STR97##          S[2,3-dihydroxypropoxycarbonyl) methyl]5-[2-chloro-4-(                         trifluoro- methyl)phenoxy]-2-nitro- benzenecarbothioat                         e                                                            SCH.sub.2 CHCHCOOC.sub.2 H.sub.5                                                                 S[(3-ethoxycarbonyl)propen-2-yl]                                               5-[2-chloro-4-(trifluoromethyl)                                                phenoxy]-2-nitrobenzene-                                                       carbothioate                                                ##STR98##          1,1 dimethyl-2,2,2-trichloro- ethoxycarbonyl                                   5-[2-chloro-4- (trifluoromethyl)phenoxy]-2- nitrobenzo                         ate                                                         ##STR99##          5-[2-chloro-4-(trifluoromethyl) phenoxy]-2-nitrobenzoy                         l Oethylphosphonic acid ammonium salt                        CCl.sub.3         1-{5-[2-chloro-4-(trifluoromethyl)                                             phenoxy]-2-nitrophenyl}2,2,2,-                                                 trichloroethanone                                            CF.sub.3          1-{5-[2-chloro-4-(trifluoromethyl)                                             phenoxy]-2-nitrophenyl}2,2,2,-                                                 trifluoroethanone                                           ##STR100##         dimethyl 5-[2-chloro-4-trifluoro- methyl)phenoxy]-2-ni                         trobenzoyl- methylphosphonate                               ##STR101##         {5-[2-chloro-4-(trifluoromethyl) phenoxy]2-nitrophenyl                         }4-methoxy- 3-methylphenyl methanone                        ##STR102##         1-{5-[2-chloro-4-(trifluoromethyl) phenoxy]-2-nitrophe                         nyl}2-(di- methoxyphosphonylmethyl- amino)ethanone            CN               5-[2-chloro-4-(trifluoromethyl)                                                phenoxy]-2-nitrobenzoyl cyanide                            __________________________________________________________________________

    ______________________________________                                         Miscellaneous - Amide                                                          QA              Compound Name                                                  ______________________________________                                         NHCH.sub.2 CH(OCH.sub.3).sub.2                                                                 N(2,2-dimethoxyethyl)5-                                                        [2-chloro-4-trifluoromethyl)                                                   phenoxy]-2-nitrobenzamide                                       ##STR103##     N(carboxymethyl)-N (phosphonomethyl)5-[2-chloro-4-                             (trifluoromethyl)phenoxy]-2- nitrobenzamide                     ##STR104##     N(carboxymethoxy)5-[2-chloro-4- (trifluoromethyl)phenoxy]-                     2- nitrobenzamide                                               ##STR105##     N(1-methylethyl)-N phenylmethyl)5-[2-chloro-4- (trifluorom                     ethyl)phenoxy]-2- nitrobenzamide                                ##STR106##     3{5-[2-chloro-4-(trifluoromethyl) phenoxy]-2-nitrobenzoyl}                     4-chloro- 2-oxobenzothiazoline                                  ##STR107##     N[1,3-dihydroxy-2-methylpropyl) 5-[2-chloro-4-(trifluorome                     thyl) phenoxy]-2-nitrobenzamide                                 ##STR108##     N(diethoxyphosphonyl)5-[2- chloro-4-(trifluoromethyl)pheno                     xy]- 2-nitrobenzamide                                            NHCH.sub.2 CH.sub.2 SO.sub. 3 Na                                                             N(2-sulfoethyl)5-[2-chloro-4-                                                  (trifluoromethyl)phenoxy]-2-                                                   nitrobenzamide sodium salt                                       NHCH.sub.2 SO.sub.3 C.sub.6 H.sub.13                                                         N(2-hexyloxysulfonyl)ethyl                                                     5-[2-chloro-4-(trifluoromethyl)                                                phenoxy]-2-nitrobenzamide                                       ##STR109##     N(trifluoroacetyl)5-[2-chloro-4- (trifluoromethyl)phenoxy]                     -2- nitrobenzamide                                              ##STR110##     N(4-sulfophenyl)5-[2-chloro- 4-(trifluoromethyl)phenoxy]-2                     - nitrobenzamide                                                 NHC(CH.sub.3).sub.2 CN                                                                       N[(1-cyano-1-methyl)-2-ethyl]                                                  4-[2-chloro-4-(trifluoromethyl)                                                phenoxy]-2-nitrobenzamide                                       ##STR111##     N(ethoxycarbonyl)5-[2-chloro- 4-(trifluoromethyl)phenoxy]-                      2-nitrobenzamide                                               ##STR112##     N[2-methyl-4-(phenylsulfonyl) phenyl]5-[2-chloro-4-(triflu                     oro- methyl)phenoxy]-2-nitrobenzamide                           ##STR113##     N(4-aminophenylsulfonyl)-N (methoxycarbonyl) 5-[2-chloro-4                     -(trifluoromethyl) phenoxy]-2-nitrobenzamide                     NHCHNOH       N[(hydroxyimino)methyl]                                                        5-[2-chloro-4-(trifluoromethyl)                                                phenoxy]-2-nitrobenzamide                                        NHNH.sub. 2   5-[2-chloro-4-(trifluoromethyl)                                                phenoxy]-2-nitrobenzoic acid                                                   hydrazide                                                       ##STR114##     5-[2-chloro-4-(trifluoromethyl) phenoxy]-2-nitrobenzoic                        acid methyl hydrazide                                           ##STR115##     5-[2-chloro-4-(trifluoromethyl) phenoxy]-2-nitrobenzoyl(2-                     chloro- acetyl)hydrazide                                        ##STR116##     5-[2-chloro-4-(trifluoromethyl) phenoxy]-2-nitrobenzoyl                        2-(carbox- amido)hydrazide                                       NHCN          5-[2-chloro-4-(trifluoromethyl)-                                               phenoxy]-2-nitrobenzoylcyanamide                                ##STR117##     5-[2-chloro-4-(trifluoromethyl)- phenoxy]-2-nitrobenzoylcy                     anamide sodium salt                                              N.sub.3       5-[2-chloro-4-(trifluoromethyl)                                                phenoxy]-2-nitrobenzoyl amide                                    ONCHNH.sub.2  aminomethyleneamino 5-[2-chloro-                                               4-(trifluoromethyl)phenoxy]-2                                                  nitrobenzoate                                                    ONC(CH.sub.3).sub.2                                                                          1-methylethylideneimino 5-[2-                                                  chloro-4-(trifluoromethyl)                                                     phenoxy]-2-nitrobenzoate                                        ##STR118##     1-(methylthio)ethylideneamino 5[2-chloro-4-(trifluoromethy                     l) phenoxy]-2-nitrobenzoate                                    ______________________________________                                    

Primary Herbicide Screening

The compounds of this invention can be applied in various ways to achieve herbicidal action. They can be applied per se, as solids or in vaporized form, but are preferably applied as the toxic components in pesticidal compositions of the compound and a carrier. These compositions are preferably applied directly to the soil and often incorporated therewith. The compositions can be applied as granulars or dusts; as liquid sprays, or as gas-propelled sprays and can contain, in addition to a carrier, additives such as emulsifying agents, binding agents, gases compressed to the liquid state, odorants, stabilizers, and the like. A wide variety of liquid and solid carriers can be used. Non-limiting examples of solid carriers include talc, bentonite, diatomaceous earth, pyrophyllite, fullers earth, gypsum, flours derived from cotton seeds and nut shells, and various natural and synthetic clays having a pH not exceeding about 9.5. Non-limiting examples of liquid carriers include water, organic solvents such as alcohols, ketones, light oils, and medium oils and vegetable oils such as cottonseed oil.

In practice, herbicidal application is measured in terms of pounds of herbicide applied per acre. The compounds of this invention are effective herbicides when applied in herbicidal amounts, i.e., at rates between about 0.03 pounds and about 10 pounds per acre.

HERBICIDAL EFFECTIVENESS

Method of Propagating Test Species

Crop and weed species are planted in 8"×10" disposable fiber flats containing potting soil to provide each flat with a 4" row of all test species. Crop species consist of field corn (CN), crabgrass (CG), cotton (CT), and soybeans (SB). The weed species consist of foxtail millet (FM), green foxtail (CF), velvetleaf (VL), cocklebur (CB), wild mustard (WM) and pigweed (FW).

Cotton, corn, soybean, and cocklebur plantings consist of 4 to 5 seeds per row depending upon species. The smaller seeded species (velvetleaf, wild mustard, pigweed, foxtail millet and green foxtail) are planted in an uncounted but sufficient number to provide a solid row of seedlings.

Plantings for the pre- and post-emergence portions of the test are identical as to seeding. The initial watering until emergence is done from the top. The post-emergence phase is propagated in advance so as to provide plants of the proper stage of development at the time of treatment. Plantings for the pre-emergence phase are made not more than one day in advance of treatment.

The desired stage of development for treatment of the post-emergence broadleaf species (CT, SB, CB, VL, WM, PW) is the one true leaf or first trifoliate leaf stage. The desired stage for corn would be a height of 3-4", while a 2" height would be adequate for the grasses.

Method of Treatment

Spray applications are made with a handgun sprayer (aspirator type) simultaneously to one flat of established plants for the post-emergence phase and one newly seeded flat for the pre-emergence phase. The 10 lb./acre treatment rate consists of the uniform application of 116 milligrams of test compound to the combined area of the two flats (160 sq. inches). Application is made in a solvent mixture consisting of 40 ml acetone and 40 ml water and a surfactant concentration of 0.1%.

Following spray application, flats are returned to the greenhouse where watering of the post-emergence phase is done only by subirrigation. The pre-emergence phase is top watered by sprinkling until after test species have emerged. Subsequent watering is by-subirrigation.

Two weeks after treatment, the pre- and post-emergence injury and control is rated on a 0-100% injury and control scale. Special physiological effects are rated as to intensity also at this time.

The herbicidal test data reported for compounds 1-81 was obtained at application rates of 10 lbs. down to 1/4 lb./acre. The following lists the metric equivalents for each rate.

    ______________________________________                                         Application Rate                                                               US - lb./acre Metric - kg/ha                                                   ______________________________________                                         10.0          11.2                                                             4.0           4.48                                                             2.0           2.24                                                             1.0           1.12                                                             0.5           0.56                                                             0.25          0.28                                                             ______________________________________                                    

Test results are set forth in Table I (pre-emergence) and Table II (post-emergence).

                                      TABLE I                                      __________________________________________________________________________        Dosage                                                                      Cpd.                                                                              Lbs./                                                                              Pre-Emergence                                                           No.                                                                               Acre                                                                               CG  FM  GF  VL  CB  WM  PW  CT CN SB                                    __________________________________________________________________________     1  10  --  100 90  90  0   100 100 10 0  0                                        4   --  100 90  20  --  100 --  0  0  0                                        2   --  100 60  10  --  100 70  0  10 10                                       1   --  90  90  30  0   100 100 20 0  10                                       1/2 --  90  80  0   0   90  100 20 0  10                                       1/4 --  90  70  30  0   90  80  0  10 0                                     2  10  --  20  20  10  0   70  90  0  0  0                                        4   --  --  --  --  --  --  --  -- -- --                                       2   --  --  --  --  --  --  --  -- -- --                                       1   --  --  --  --  --  --  --  -- -- --                                       1/2 --  --  --  --  --  --  --  -- -- --                                       1/4 --  --  --  --  --  --  --  -- -- --                                    3  10  --  90  90  0   0   90  100 0  0  0                                        4   --  100 90  30  20  90  100 10 0  0                                        2   --  60  10  0   10  30  80  -- 0  0                                        1   --  --  --  --  --  --  --  -- -- --                                       1/2 --  --  --  --  --  --  --  -- -- --                                       1/4 --  --  --  --  --  --  --  -- -- --                                    4  10  --  100 90  90  20  100 100 10 0  10                                       4   --  100 90  0   --  100 --  0  0  10                                       2   --  90  40  0   --  70  60  0  0  0                                        1   --  --  --  --  --  --  --  -- -- --                                       1/2 --  --  --  --  --  --  --  -- -- --                                       1/4 --  --  --  --  --  --  --  -- -- --                                    5  4   --  90  90  70  30  100 100 60 0  0                                        2   --  90  90  10  40  100 100 20 0  10                                       1   --  70  10  0   0   70  100 0  0  10                                       1/2 --  --  --  --  --  --  --  -- -- --                                       1/4 --  --  --  --  --  --  --  -- -- --                                    6  4   --  100 90  70  20  100 100 0  40 0                                        2   --  100 90  10  0   100 100 40 0  0                                        1   --  90  60  0   40  90  90  30 0  0                                        1/2 --  70  80  10  0   50  90  10 0  10                                       1/4 --  20  0   10  10  30  0   0  20 10                                    7  4   --  0   0   0   0   100 100 40 0  0                                        2   --  70  20  0   0   0   70  0  0  0                                        1   --  --  --  --  --  --  --  -- -- --                                       1/2 --  --  --  --  --  --  --  -- -- --                                       1/4 --  --  --  --  --  --  --  -- -- --                                    8  10  --  0   0   0   0   0   0   0  30 0                                        4   --  --  --  --  --  --  --  -- -- --                                       2   --  --  --  --  --  --  --  -- -- --                                    9  4   --  0   0   0   --  10  60  10 0  0                                        2   --  --  --  --  --  --  --  -- -- --                                       1   --  --  --  --  --  --  --  -- -- --                                       1/2 --  10  0   0   0   50  60  0  0  0                                        1/4 --  --  --  --  --  --  --  -- -- --                                    10 4   --  10  10  10  0   0   0   10 10 10                                       2   --  --  --  --  --  --  --  -- -- --                                    11 10  --  0   0   0   0   0   0   0  0  0                                        4   --  --  --  --  --  --  --  -- -- --                                    12 4   --  100 90  90  60  100 100 40 10 0                                        2   --  100 90  40  10  100 100 10 30 0                                        1   --  100 90  0   0   100 100 0  0  0                                        1/2 --  70  30  10  0   90  90  30 0  0                                        1/4 --  20  20  0   0   20  60  60 60 30                                    13 10  --  90  90  100 80  100 100 90 10 10                                       4   --  90  90  70  10  90  90  10 20 0                                        2   --  90  70  30  0   90  90  0  0  0                                        1   --  --  --  --  --  --  --  -- -- --                                       1/2 --  --  --  --  --  --  --  -- -- --                                       1/4 --  --  --  --  --  --  --  -- -- --                                    14 4   --  70  50  10  0   70  60  0  20 0                                        1   --  --  --  --  --  --  --  -- -- --                                       1/2 --  --  --  --  --  --  --  -- -- --                                       1/4 --  --  --  --  --  --  --  -- -- --                                    15 4   --  100 90  40  20  90  90  10 0  0                                        2   --  90  90  10  0   90  90  0  0  0                                        1   --  70  60  10  0   20  80  20 0  10                                       1/2 --  --  --  --  --  --  --  -- -- --                                       1/4 --  --  --  --  --  --  --  -- -- --                                    16 4   --  90  50  10  0   90  70  10 10 0                                        2   --  80  10  10  0   70  0   0  0  10                                       1   --  --  --  --  --  --  --  -- -- --                                       1/2 --  --  --  --  --  --  --  -- -- --                                       1/4 --  --  --  --  --  --  --  -- -- --                                    17 4   --  100 90  40  0   100 100 0  10 0                                        2   --  90  90  30  0   90  90  30 0  10                                       1   --  --  --  --  --  --  --  -- -- --                                       1/2 --  --  --  --  --  --  --  -- -- --                                       1/4 --  --  --  --  --  --  --  -- -- --                                    18 10  --  100 80  70  0   100 100 10 0  0                                        2   --  100 40  20  10  100 100 10 0  10                                       1/2 --  90  20  0   10  100 90  10 10 30                                       1/4 --  10  10  40  10  80  60  10 0  0                                     19 10  --  100 100 80  60  100 100 30 60 0                                        2   --  100 70  40  10  100 100 20 10 10                                       1/2 --  100 60  0   0   100 60  10 0  0                                        1/4 --  10  10  60  20  70  50  20 0  20                                    20 4   --  90  80  50  0   100 90  0  0  0                                        2   --  80  20  10  20  90  20  0  0  10                                       1   --  0   0   0   0   0   20  30 10 10                                       1/2 --  --  --  --  --  --  --  -- -- --                                       1/4 --  --  --  --  --  --  --  -- -- --                                    21 4   --  80  60  20  0   30  20  10 20 20                                       2   --  --  --  --  --  --  --  -- -- --                                    22 4   --  90  80  20  0   90  90  0  10 0                                        2   --  80  70  20  0   80  60  0  20 0                                        1   --  90  20  10  20  30  10  40 10 50                                       1/4 --  --  --  --  --  --  --  -- -- --                                    23 4   --  80  0   10  0   90  30  10 0  0                                        2   --  70  10  30  0   70  10  0  0  0                                        1/2 --  --  --  --  --  --  --  -- -- --                                       1/4 --  --  --  --  --  --  --  -- -- --                                    24 4   --  90  70  60  10  90  90  0  0  10                                       2   --  80  70  40  0   70  80  0  0  0                                        1/2 --  0   10  0   0   0   10  0  0  0                                        1/4 --  --  --  --  --  --  --  -- -- --                                    25 4   --  100 90  90  20  100 100 10 40 10                                       2   --  90  90  80  40  100 100 40 10 20                                       1   --  100 90  10  0   90  90  0  0  0                                        1/2 --  90  70  0   0   90  70  10 0  10                                       1/4 --  10  20  10  0   20  20  0  0  0                                     26 2   --  40  40  20  70  90  70  0  0  10                                       1/2 --  10  0   10  0   90  40  0  0  0                                        1/4 --  --  --  --  --  --  --  -- -- --                                    27 2   --  90  90  80  0   100 100 10 0  0                                        1/2 --  70  50  40  0   90  100 0  0  0                                        1/4 --  50  10  0   0   70  10  0  0  0                                     28 2   --  90  90  90  20  100 100 50 10 20                                       1/2 --  90  90  20  0   100 100 10 0  0                                        1/4 --  60  20  0   --  50  80  10 0  0                                     29 2   --  100 100 40  10  100 100 0  0  20                                       1/2 --  100 90  0   0   100 90  10 0  0                                        1/4 --  10  40  60  0   90  90  0  0  0                                     30 1/2 10  60  --  30  --  90  90  -- -- --                                       1/4 10  40  --  10  --  10  --  -- -- --                                    31 2   --  60  50  10  0   80  90  30 20 0                                        1/2 --  10  0   10  0   10  50  0  0  0                                        1/4 --  --  --  --  --  --  --  -- -- --                                    32 2   --  90  70  0   0   100 100 10 0  10                                       1/2 --  90  90  0   0   90  80  0  0  10                                       1/4 --  30  10  0   0   10  0   0  0  0                                     33 2   --  100 90  50  0   90  90  10 10 40                                       1/2 --  80  10  0   0   20  10  0  0  0                                        1/4 --  --  --  --  --  --  --  -- -- --                                    34 2   --  100 100 10  30  90  90  30 10 0                                        1/2 --  20  20  20  10  80  20  0  0  0                                        1/4 --  --  --  --  --  --  --  -- -- --                                    36 2   --  50  20  40  --  20  90  10 20 30                                       1/2 --  0   0   0   --  20  50  10 10 10                                       1/4 --  --  --  --  --  --  --  -- -- --                                    37 2   --  60  60  0   --  80  20  0  0  0                                        1/2 --  0   0   0   --  0   0   0  0  0                                        1/4 --  --  --  --  --  --  --  -- -- --                                    38 2   --  100 90  50  10  100 100 60 0  0                                        1/2 --  90  50  0   0   50  40  0  0  0                                        1/4 --  --  --  --  --  --  --  -- -- --                                    39 2   --  90  90  70  20  100 100 10 20 0                                        1/2 --  90  70  10  10  100 100 0  0  0                                     40 2   --  100 90  90  0   100 100 10 10 0                                        1/2 --  90  70  20  0   100 90  10 0  0                                     41 2   --  100 90  40  0   100 90  10 0  0                                        1/2 --  90  30  0   0   90  70  0  0  0                                        1/4 --  0   0   0   0   10  10  0  0  0                                     42 2   --  100 100 90  70  100 100 90 20 30                                       1/2 --  100 100 80  60  100 100 90 20 30                                       1/4 --  80  90  10  0   60  90  10 0  10                                    43 1/2 90  90  --  50  0   90  100 -- -- --                                       1/4 60  90  --  50  --  10  --  -- -- --                                    44 2   --  100 100 90  30  100 100 60 20 30                                       1/2 --  90  90  80  10  100 100 20 10 20                                       1/4 --  20  0   0   0   90  20  0  0  10                                    45 2   --  100 100 70  10  100 100 10 10 0                                        1/2 --  90  80  10  0   100 100 0  0  0                                        1/4 --  90  10  0   0   80  90  0  0  0                                     46 2   --  100 90  20  10  100 90  10 0  0                                        1/2 --  90  90  10  30  90  70  10 0  0                                        1/4 --  30  20  0   0   0   0   0  0  0                                     47 2   --  100 90  90  20  100 100 30 10 0                                        1/2 --  100 90  20  10  100 100 10 0  0                                        1/4 --  20  0   0   0   90  90  20 10 0                                     48 2   --  100 100 70  100 100 0   0  0  0                                        1/2 --  100 90  30  0   90  60  40 0  0                                     49 2   --  90  90  60  0   90  100 0  0  0                                        1/2 --  20  0   10  10  100 90  0  0  10                                    50 2   --  90  90  90  50  100 100 50 10 30                                       1   --  90  90  20  0   100 90  0  0  0                                        1/2 --  80  70  10  0   100 90  10 10 20                                       1/4 --  90  70  20  10  90  80  0  0  0                                     51 10  --  100 100 100 50  100 100 10 30 0                                        4   --  100 100 90  60  100 100 20 10 20                                       2   --  90  90  70  10  100 100 20 0  10                                       1   --  100 100 10  0   100 100 0  0  10                                       1/2 --  90  50  0   10  70  40  0  0  0                                        1/4 --  --  --  --  --  --  --  -- -- --                                    52 10  100 100 --  90  --  100 --  -- -- --                                       1   60  70  --  60  0   90  --  -- -- --                                       1/2 40  80  --  50  10  80  --  -- -- --                                       1/4 --  --  --  --  --  --  --  -- -- --                                    53 10  --  90  90  50  --  100 100 50 10 0                                        4   --  90  90  30  --  100 100 10 0  0                                        1   --  90  60  0   --  90  90  0  0  0                                        1/2 --  10  0   10  --  20  90  0  0  0                                        1/4 --  --  --  --  --  --  --  -- -- --                                    54 4   --  0   0   0   0   0   0   0  0  0                                        2   --  --  --  --  --  --  --  -- -- --                                       1   --  --  --  --  --  --  --  -- -- --                                       1/2 --  --  --  --  --  --  --  -- -- --                                       1/4 --  --  --  --  --  --  --  -- -- --                                    55 4   --  0   20  40  10  90  100 60 0  20                                       2   --  0   0   0   0   0   0   0  0  0                                        1   --  --  --  --  --  --  --  -- -- --                                       1/2 --  --  --  --  --  --  --  -- -- --                                       1/4 --  --  --  --  --  --  --  -- -- --                                    56 4   --  0   0   30  --  70  100 30 0  0                                        2   --  --  --  --  --  --  --  -- -- --                                    57 4   --  10  0   0   --  70  90  0  0  0                                        2   --  --  --  --  --  --  --  -- -- --                                       1   --  --  --  --  --  --  --  -- -- --                                       1/2 --  --  --  --  --  --  --  -- -- --                                       1/4 --  --  --  --  --  --  --  -- -- --                                    58 4   --  30  0   0   --  10  100 0  0  0                                        2   --  --  --  --  --  --  --  -- -- --                                       1   --  --  --  --  --  --  --  -- -- --                                    59 10  --  0   0   0   --  0   100 0  0  0                                     60 10  --  0   0   10  0   10  70  0  0  0                                        4   --  --  --  --  --  --  --  -- -- --                                    61 2   --  50  20  60  10  90  80  20 10 20                                       1/2 --  0   0   0   0   50  0   0  0  0                                        1/4 --  --  --  --  --  --  --  -- -- --                                    62 4   90  100 --  80  --  100 100 -- -- --                                       1   90  40  --  70  --  100 100 -- -- --                                       1/2 40  0   --  10  0   80  --  -- -- --                                    63 4   90  90  --  100 --  100 100 -- -- --                                       1   60  40  --  70  --  90  0   -- -- --                                       1/2 20  0   --  20  0   10  0   -- -- --                                    64 4   90  90  --  90  --  100 100 -- -- --                                       2   90  90  --  50  --  100 90  -- -- --                                       1   20  0   --  40  0   90  0   -- -- --                                       1/2 0   20  --  0   0   70  70  -- -- --                                    65 4   80  90  --  90  --  100 --  -- -- --                                       2   --  30  70  20  0   80  100 0  0  0                                        1   --  90  70  80  0   90  90  10 10 0                                        1/2 --  10  10  50  0   100 100 0  0  0                                        1/4 --  30  10  10  0   70  80  0  0  0                                     66 4   90  90  --  100 --  100 100 -- -- --                                       1   70  40  --  70  --  100 100 -- -- --                                       1/2 0   10  --  20  0   60  0   -- -- --                                    67 4   90  90  --  90  --  100 100 -- -- --                                       2   60  70  --  60  --  90  90  -- -- --                                       1   0   0   --  10  0   40  0   -- -- --                                       1/2 0   0   --  40  10  90  20  -- -- --                                    68 10  100 90  --  100 --  100 100 -- -- --                                       4   --  100 90  90  60  100 100 0  10 0                                        2   --  90  90  90  10  100 100 20 20 20                                       1   --  90  30  90  0   100 100 40 0  0                                        1/2 --  70  80  70  50  100 100 10 0  0                                        1/4 --  80  60  0   0   100 100 20 0  --                                    69 2   --  100 90  60  50  100 100 10 40 20                                       1/2 --  100 90  10  10  100 100 0  0  10                                       1/4 --  0   60  10  10  80  80  10 50 10                                    70 2   --  100 90  50  50  100 100 10 10 20                                       1/2 --  100 90  10  30  100 100 20 0  10                                       1/4 --  0   10  50  0   90  90  0  40 80                                    71 2   --  90  50  40  0   90  80  10 10 10                                       1/2 --  10  10  0   0   10  90  10 0  10                                       1/4 --  --  --  --  --  --  --  -- -- --                                    72 10  --  90  90  --  20  90  90  -- 40 70                                       2   --  90  90  70  0   100 100 10 20 0                                        1   --  90  80  0   0   90  80  10 0  0                                        1/2 --  20  0   10  --  90  90  20 20 10                                       1/4 --  30  0   10  --  70  80  0  20 10                                    73 10  --  100 90  90  30  100 100 20 60 0                                        4   --  100 90  80  60  100 90  50 70 10                                       2   --  80  70  70  10  100 10  10 0  0                                        1   --  90  60  10  0   90  60  20 0  10                                       1/2 --  90  50  0   0   90  80  0  0  0                                     74 2   --  90  90  70  0   100 100 10 10 0                                        1/2 --  90  70  0   0   90  50  10 0  0                                        1/4 --  0   0   10  0   70  70  10 0  10                                    75 2   --  60  20  0   0   50  80  0  0  0                                        1   --  --  --  --  --  --  --  -- -- --                                       1/2 --  --  --  --  --  --  --  -- -- --                                       1/4 --  --  --  --  --  --  --  -- -- --                                    76 2   --  80  40  80  0   70  70  20 60 10                                       1/2 --  10  10  0   0   70  70  10 0  0                                        1/4 --  --  --  --  --  --  --  -- -- --                                    77 2   --  100 90  10  0   100 90  0  0  0                                        1/2 --  90  70  0   10  90  60  10 0  0                                     78 10  90  90  --  100 --  100 --  -- -- --                                       4   --  90  90  90  0   100 100 0  0  0                                        2   --  90  90  80  0   90  100 10 0  0                                        1   --  40  60  60  10  100 100 0  0  0                                        1/2 --  50  70  0   --  90  90  0  0  0                                        1/4 --  80  50  20  0   90  60  10 30 0                                     79 10  70  90  --  50  --  90  --  -- -- --                                       1/4 0   0   --  0   --  0   --  -- -- --                                    80 4   --  100 90  40  20  90  90  0  20 10                                       2   --  90  80  10  10  90  10  10 10 10                                       1   --  10  0   0   0   70  20  0  0  0                                        1/2 --  --  --  --  --  --  --  -- -- --                                       1/4 --  --  --  --  --  --  --  -- -- --                                    81 2   --  80  50  0   0   90  80  0  0  0                                        1/2 --  10  0   0   0   10  60  0  0  0                                        1/4 --  --  --  --  --  --  --  -- -- --                                    __________________________________________________________________________

                                      TABLE II                                     __________________________________________________________________________        Dosage                                                                      Cpd.                                                                              Lbs./                                                                              Post-Emergence                                                          No.                                                                               Acre                                                                               CG  FM  GF  VL  CB  WM  PW  CT  CN  SB                                  __________________________________________________________________________     1  10  --  100 100 100 100 100 100 100 80  60                                     4   --  90  90  100 100 100 100 90  60  50                                     2   --  100 100 100 --  100 --  90  50  20                                     1   --  100 90  100 --  100 100 90  30  50                                     1/2 --  100 90  90  90  100 100 80  70  10                                     1/4 --  50  50  40  80  100 100 60  50  40                                  2  10  --  90  90  90  80  90  100 90  10  10                                     4   --  100 90  90  60  90  90  90  10  10                                     2   --  90  90  90  80  100 100 90  20  20                                     1   --  90  90  80  90  90  100 90  70  70                                     1/2 --  80  70  60  90  100 100 90  80  30                                     1/4 --  90  70  70  80  100 80  90  50  60                                  3  10  --  90  90  90  90  100 100 100 30  30                                     4   --  100 100 90  90  100 100 90  30  10                                     2   --  100 90  100 90  100 100 90  90  20                                     1   --  90  90  90  90  100 100 80  70  60                                     1/2 --  90  90  90  90  100 90  90  90  60                                     1/4 --  90  80  90  80  100 100 90  30  10                                  4  10  --  100 100 100 100 100 100 100 90  50                                     4   --  100 100 100 --  100 --  100 90  30                                     2   --  90  90  100 100 100 100 100 20  20                                     1   --  100 100 100 --  100 100 100 40  50                                     1/2 --  100 90  90  90  100 100 100 70  10                                     1/4 --  50  70  30  50  90  100 40  30  50                                  5  4   --  100 90  100 100 100 100 90  0   40                                     2   --  90  90  100 --  100 --  90  10  20                                     1   --  90  90  100 0   100 100 90  50  10                                     1/2 --  80  70  90  80  100 100 90  20  20                                     1/4 --  60  60  50  70  90  100 60  30  60                                  6  4   --  100 100 100 100 100 100 100 10  60                                     2   --  100 100 100 100 100 100 90  80  40                                     1   --  70  80  70  70  100 100 60  70  60                                     1/2 --  90  90  90  90  100 90  80  80  20                                     1/4 --  80  60  80  50  90  70  90  10  10                                  7  4   --  100 80  100 80  100 100 80  0   20                                     2   --  90  30  100 --  90  100 90  10  20                                     1   --  90  70  100 --  90  100 90  --  40                                     1/2 --  90  90  100 --  90  100 90  10  50                                     1/4 --  90  90  90  50  100 100 60  30  40                                  8  10  --  90  80  100 60  90  100 40  0   20                                     4   --  60  30  --  --  70  --  70  20  0                                      2   --  80  70  50  --  70  70  90  0   10                                  9  4   --  90  90  100 40  90  100 90  10  20                                     2   --  90  90  90  --  90  100 90  10  30                                     1   --  90  90  100 80  100 100 90  0   10                                     1/2 --  100 90  90  70  100 100 80  10  10                                     1/4 --  70  80  30  50  90  100 50  50  40                                  10 4   --  80  20  70  10  90  50  90  40  10                                     2   --  50  50  70  0   90  70  90  70  30                                  11 10  --  90  90  70  30  80  100 40  0   10                                     4   --  30  20  30  20  70  90  80  30  10                                  12 4   --  90  90  100 90  100 100 90  20  10                                     2   --  100 100 90  100 100 100 100 70  40                                     1   --  100 100 100 100 100 100 100 60  10                                     1/2 --  100 100 90  80  100 100 80  80  60                                     1/4 --  90  90  90  70  100 100 90  60  50                                  13 10  --  90  90  100 100 100 100 90  80  20                                     4   --  100 100 100 100 100 100 100 90  90                                     2   --  100 100 90  90  100 100 100 90  50                                     1   --  90  90  90  70  100 100 90  70  50                                     1/2 --  90  90  80  70  100 100 90  70  60                                     1/4 --  90  80  80  80  100 90  90  60  60                                  14 4   --  90  90  90  80  100 100 90  30  20                                     1   --  90  90  80  10  90  90  90  70  40                                     1/2 --  90  90  70  70  90  90  80  70  20                                     1/4 --  80  80  70  50  90  100 80  50  70                                  15 4   --  90  100 100 90  100 100 100 60  10                                     2   --  90  90  90  90  100 90  90  70  30                                     1   --  90  90  80  60  90  100 90  50  30                                     1/2 --  90  90  90  90  100 100 90  50  30                                     1/4 --  90  70  60  50  70  90  70  50  70                                  16 4   --  90  90  60  50  100 100 90  50  10                                     2   --  30  40  60  30  90  80  70  50  80                                     1   --  70  60  70  70  90  90  90  60  70                                     1/2 --  90  70  70  80  100 100 90  60  40                                     1/4 --  60  40  60  30  90  100 60  50  50                                  17 4   --  100 100 100 90  100 100 90  70  30                                     2   --  100 100 100 90  100 100 100 80  40                                     1   --  90  90  80  60  90  100 70  70  40                                     1/2 --  90  90  90  90  90  90  90  70  10                                     1/4 --  80  80  80  50  90  60  90  40  10                                  18 10  --  100 100 100 90  100 100 90  90  90                                     2   --  90  90  100 90  100 100 90  90  80                                     1/2 --  90  90  100 70  100 100 80  70  60                                     1/4 --  90  70  90  50  100 100 70  70  50                                  19 10  --  100 100 100 90  100 100 90  80  40                                     2   --  90  90  100 100 100 100 90  60  40                                     1/2 --  90  90  90  90  100 100 90  80  40                                     1/4 --  90  70  70  40  100 100 50  60  20                                  20 4   --  90  90  90  80  100 100 90  40  20                                     2   --  70  80  90  70  90  90  90  60  40                                     1   --  80  60  70  70  90  80  90  50  20                                     1/2 --  20  20  60  30  90  90  90  30  30                                     1/4 --  50  40  40  40  100 50  50  40  50                                  21 4   --  80  70  90  40  90  90  90  50  20                                     2   --  10  20  70  70  80  70  70  30  30                                  22 4   --  90  90  90  70  90  100 90  80  30                                     2   --  80  80  90  20  90  100 90  80  50                                     1   --  90  90  70  40  90  --  60  50  70                                     1/4 --  50  60  10  10  80  80  50  10  10                                  23 4   --  90  90  80  60  90  100 90  80  80                                     2   --  90  90  90  70  90  --  90  40  40                                     1/2 --  20  20  20  10  90  80  80  10  10                                     1/4 --  70  70  30  20  80  70  80  10  30                                  24 4   --  100 100 100 90  100 100 90  90  90                                     2   --  100 100 100 80  100 --  90  50  70                                     1/2 --  60  50  70  20  80  100 90  20  30                                     1/4 --  70  80  70  50  90  90  90  10  40                                  25 4   --  100 100 100 100 100 100 100 90  80                                     2   --  --  --  --  --  --  --  --  --  --                                     1   --  100 100 100 90  100 90  100 90  70                                     1/2 --  90  90  90  90  100 100 100 90  90                                     1/4 --  80  80  90  80  90  90  90  40  30                                  26 2   --  50  70  100 90  100 100 90  30  60                                     1/2 --  10  0   90  50  90  90  50  20  40                                     1/4 --  20  10  60  80  90  100 50  10  50                                  27 2   --  100 100 100 100 100 100 90  70  90                                     1/2 --  100 100 100 90  100 100 90  60  60                                     1/4 --  70  60  90  70  100 60  90  50  80                                  28 2   --  100 90  100 100 100 100 100 90  90                                     1/2 --  90  90  90  90  100 100 90  90  60                                     1/4 --  90  90  90  80  100 100 100 70  80                                  29 2   --  100 100 100 90  100 100 100 60  90                                     1/2 --  90  90  100 80  100 100 90  10  80                                     1/4 --  90  90  100 70  100 100 90  50  80                                  30 1/2 20  100 --  --  --  100 100 90  80  60                                     1/4 90  90  --  70  100 100 100 90  20  40                                  31 2   --  90  90  100 90  100 100 90  30  60                                     1/2 --  90  90  100 70  90  100 90  60  30                                     1/4 --  80  80  100 60  80  100 80  30  70                                  32 2   --  100 100 100 90  100 100 100 40  80                                     1/2 --  100 100 100 80  100 100 100 20  80                                     1/4 --  30  20  100 90  90  90  70  60  40                                  33 2   --  100 100 100 90  100 100 100 70  80                                     1/2 --  90  90  100 70  100 100 100 70  80                                     1/4 --  80  70  90  90  100 100 70  10  40                                  34 2   --  70  70  100 90  100 100 90  60  60                                     1/2 --  60  60  100 90  100 100 80  40  40                                     1/4 --  90  70  90  90  100 100 50  20  50                                  36 2   --  100 90  90  80  100 100 90  90  50                                     1/2 --  90  90  90  30  90  100 90  70  60                                     1/4 --  20  30  90  --  90  90  90  40  10                                  37 2   --  90  90  80  0   90  90  90  80  70                                     1/2 --  90  90  90  --  90  90  90  40  40                                     1/4 --  10  10  70  --  80  70  50  10  30                                  38 2   --  90  90  100 90  100 100 90  50  60                                     1/2 --  90  90  100 90  100 100 60  10  50                                     1/4 --  30  20  90  80  100 100 70  10  10                                  39 2   --  90  90  100 100 100 100 100 60  90                                     1/2 --  90  90  90  90  100 100 100 40  70                                  40 2   --  100 100 100 100 100 100 100 90  90                                     1/2 --  90  90  100 90  100 100 100 30  70                                  41 2   --  100 100 100 100 100 100 100 90  90                                     1/2 --  90  90  100 90  100 90  90  30  80                                     1/4 --  70  80  90  70  100 90  90  20  60                                  42 2   --  100 100 100 100 100 100 100 100 90                                     1/2 --  100 100 90  90  100 100 100 90  90                                     1/4 --  100 100 100 80  100 100 90  50  80                                  43 1/2 70  100 --  90  100 100 100 100 40  40                                     1/4 100 100 --  90  100 100 100 70  40  30                                  44 2   --  100 100 100 100 100 100 100 90  90                                     1/2 --  100 100 100 90  100 100 90  80  80                                     1/4 --  90  90  90  70  100 100 90  60  60                                  45 2   --  100 100 100 100 100 100 100 100 90                                     1/2 --  100 100 90  90  100 100 100 80  60                                     1/4 --  100 100 90  90  100 100 90  50  60                                  46 2   --  100 100 100 90  100 100 100 90  90                                     1/2 --  100 100 100 70  90  90  100 70  50                                     1/4 --  90  90  90  30  90  90  90  50  50                                  47 2   --  100 100 100 100 100 100 100 90  80                                     1/2 --  90  90  70  90  100 100 90  50  30                                     1/4 --  90  90  60  20  100 100 80  20  60                                  48 2   --  100 100 100 90  100 100 100 90  80                                     1/2 --  90  90  90  90  100 100 100 40  90                                  49 2   --  50  10  90  70  100 100 60  20  30                                     1/2 --  10  20  70  30  100 100 90  40  30                                  50 2   --  90  90  60  90  100 100 90  70  40                                     1   --  90  90  100 100 100 100 80  90  60                                     1/2 --  60  80  90  70  100 100 80  0   10                                     1/4 --  90  80  90  70  100 100 40  0   30                                  51 10  --  100 100 100 80  100 100 90  70  70                                     4   --  100 100 100 100 100 100 90  90  70                                     2   --  90  90  100 90  100 100 90  70  40                                     1   --  100 100 100 100 100 100 80  90  80                                     1/2 --  60  80  100 80  100 100 90  10  20                                     1/4 --  100 90  100 70  100 90  50  0   40                                  52 10  70  90  --  100 --  100 100 80  30  30                                     1   70  40  --  100 50  100 100 80  10  40                                     1/2 30  20  --  70  20  90  100 40  10  10                                     1/4 20  90  --  30  20  100 100 70  30  10                                  53 10  100 100 --  100 90  100 100 100 90  90                                     4   100 90  --  80  80  100 100 100 70  80                                     1   90  90  --  70  60  100 100 90  60  50                                     1/2 40  40  --  20  0   100 90  80  20  50                                     1/4 20  10  --  10  --  90  50  20  10  30                                  54 4   --  30  30  80  30  100 100 40  10  10                                     2   --  20  20  10  --  90  90  20  10  10                                     1   --  80  80  90  40  90  90  50  10  20                                     1/2 --  60  50  10  --  90  90  30  10  10                                     1/4 --  20  40  30  50  80  60  40  40  10                                  55 4   --  20  20  10  20  100 100 --  0   10                                     2   --  30  30  0   --  100 80  20  0   80                                     1   --  80  80  20  30  90  100 30  20  30                                     1/2 --  80  80  10  --  90  --  80  0   10                                     1/4 --  20  30  0   30  30  30  0   0   10                                  56 4   --  80  90  50  70  100 100 20  20  10                                     2   --  30  10  30  --  60  80  70  0   10                                  57 4   --  60  80  40  30  90  100 70  0   10                                     2   --  70  40  0   --  100 100 60  10  10                                     1   --  60  50  0   --  90  90  60  40  30                                     1/2 --  20  30  20  --  90  100 50  10  20                                     1/4 --  20  20  10  30  60  80  50  10  10                                  58 4   --  40  70  0   40  90  100 30  --  20                                     2   --  10  10  0   --  90  100 10  0   10                                     1   --  50  50  30  20  70  100 30  20  30                                  59 10  --  0   10  0   0   0   80  0   0   0                                   60 10  --  80  60  10  70  90  100 30  10  10                                     4   --  20  10  10  20  80  70  50  0   10                                  61 2   --  30  20  90  60  100 100 80  30  30                                     1/2 --  20  30  80  50  100 100 70  20  30                                     1/4 --  60  60  90  70  90  100 40  20  30                                  62 4   20  20  --  0   20  100 --  30  10  20                                     1   0   10  --  10  10  60  70  30  0   30                                     1/2 30  30  --  0   10  70  50  10  0   20                                  63 4   0   0   --  0   0   90  --  20  20  30                                     1   0   30  --  20  10  50  80  10  10  20                                     1/2 20  0   --  0   0   70  60  10  0   30                                  64 4   0   20  --  10  30  30  100 60  10  10                                     2   0   10  --  20  10  100 90  70  10  10                                     1   20  20  --  10  20  80  50  20  0   10                                     1/2 10  10  --  10  10  80  60  0   10  20                                  65 4   10  20  --  30  --  100 100 70  20  40                                     2   --  70  90  100 90  100 100 90  20  10                                     1   --  90  90  100 90  100 100 80  30  40                                     1/2 --  90  90  90  --  90  100 20  10  10                                     1/4 --  50  40  70  70  90  100 80  30  40                                  66 4   0   40  --  10  20  90  100 20  40  30                                     1   0   0   --  10  50  60  50  70  0   40                                     1/2 10  10  --  20  40  40  50  10  0   40                                  67 4   20  20  --  10  60  40  100 50  40  50                                     2   10  10  --  30  50  100 100 80  10  20                                     1   20  20  --  0   10  20  100 20  10  40                                     1/2 20  0   --  10  40  30  100 10  20  20                                  68 10  20  20  --  30  --  100 100 90  20  50                                     4   --  100 100 100 100 100 100 90  90  60                                     2   --  100 90  100 100 100 100 80  60  90                                     1   --  30  50  100 --  90  100 90  20  30                                     1/2 --  90  90  100 --  90  100 90  70  90                                     1/4 --  50  40  80  80  90  100 70  30  60                                  69 2   --  100 90  100 80  100 100 90  80  70                                     1/2 --  90  90  100 70  90  90  70  40  70                                     1/4 --  50  40  100 60  90  90  90  50  60                                  70 2   --  90  80  100 70  100 100 90  70  60                                     1/2 --  90  80  100 60  100 100 90  20  50                                     1/4 --  90  70  100 50  90  90  80  20  40                                  71 2   --  40  60  100 90  100 100 90  20  60                                     1/2 --  40  40  100 90  100 100 90  10  50                                     1/4 --  20  10  60  80  90  100 50  10  50                                  72 10  --  100 100 100 100 100 100 100 90  80                                     2   --  100 100 100 90  100 100 100 80  80                                     1   --  100 100 100 90  100 100 100 80  80                                     1/2 --  90  90  90  90  100 100 90  50  80                                     1/4 --  90  90  90  80  100 100 100 30  80                                  73 10  --  100 100 100 70  100 100 90  80  50                                     4   --  90  90  100 90  100 100 90  70  40                                     2   --  30  50  70  40  100 100 50  10  30                                     1   --  40  40  50  70  90  100 50  20  30                                     1/2 --  90  90  80  70  100 100 70  20  20                                  74 2   --  90  80  90  10  100 100 90  10  40                                     1/2 --  90  80  90  --  100 90  90  20  30                                     1/4 --  60  60  80  90  90  90  90  10  40                                  75 2   --  80  70  60  20  90  100 90  10  20                                     1   --  90  80  80  40  100 70  70  20  20                                     1/2 --  20  20  50  10  90  90  90  10  10                                     1/4 --  10  10  70  --  60  20  50  0   20                                  76 2   --  20  10  40  --  90  100 90  10  50                                     1/2 --  10  10  10  --  90  90  60  10  40                                     1/4 --  10  10  80  30  80  70  40  10  10                                  77 2   --  90  90  100 90  100 100 50  20  30                                     1/2 --  90  90  90  80  100 100 30  10  30                                  78 10  60  20  --  70  --  100 100 90  70  30                                     4   --  80  90  100 90  100 100 90  0   10                                     2   --  100 100 100 90  100 100 90  50  70                                     1   --  90  90  100 60  100 100 40  80  40                                     1/2 --  90  90  90  80  90  --  30  20  20                                     1/4 --  40  80  40  50  80  100 40  40  40                                  79 10  50  60  --  80  --  100 100 80  10  20                                     1/2 70  80  --  40  80  90  100 70  10  10                                  80 4   --  90  90  100 50  100 90  90  90  30                                     2   --  70  50  90  50  90  60  90  60  90                                     1   --  70  70  80  20  90  90  90  40  10                                     1/2 --  30  30  70  50  90  90  90  60  20                                     1/4 --  50  50  40  50  80  100 50  20  50                                  81 2   --  40  40  90  70  100 100 90  30  60                                     1/2 --  30  30  100 50  100 100 90  10  40                                     1/4 --  40  40  90  30  90  90  50  10  30                                  __________________________________________________________________________

Although the present invention has been described with preferred embodiments, it is to be understood that modifications and variations may be resorted to, without departing from the spirit and scope of this invention, as those skilled in the art will readily understand. Such modifications and variations are considered to be within the purview and scope of the appended claims. 

What is claimed is:
 1. A herbicidal compound of the formula: ##STR119## wherein Q is O or S and Het is a heterocyclic ring selected from the group consisting of s-triazinyl; 2,3-dihydro-pyridazinyl; 1,2,5-thiadiazolyl; 1,3,4-thiadiazol-5-yl; 1,2-dithio-5-21; a tetrahydro-thiophene-1,1-dioxide; 2-chloro-6-pyridinyl,1,2-dihydro-1,6-dimethyl-2-oxo-4-pyridinyl with a provision that the term Q is S when Het represents 2-pyridinyl-N-oxide.
 2. A herbicidal compound as defined in claim 1, wherein Q is O.
 3. A herbicidal compound as defined in claim 1, wherein Het is: ##STR120##
 4. A herbicidal compound as defined in claim 1, wherein Het is: ##STR121##
 5. A herbicidal compound as defined in claim 2, wherein Het is: ##STR122##
 6. A herbicidal compound as defined in claim 2, wherein Het is: ##STR123##
 7. A herbicidal compound as defined in claim 2, wherein Het is: ##STR124##
 8. A herbicidal compound as defined in claim 2, wherein Het is: ##STR125##
 9. A herbicidal compound as defined in claim 1, wherein Q is S and Het is: ##STR126##
 10. A herbicidal compound as defined in claim 1, wherein Q is S and Het is: ##STR127##
 11. A herbicidal compound as defined in claim 1, wherein Q is S and Het is: ##STR128##
 12. A herbicidal compound as defined in claim 1, wherein Q is S and Het is: ##STR129##
 13. A herbicidal composition comprising a herbicidally effective amount of a compound according to claim 1 and a carrier therefor.
 14. A herbicidal comprising a herbicidally effective amount of a compound according to claim 3 and a carrier therefor.
 15. A herbicidal comprising a herbicidally effective amount of a compound according to claim 5 and a carrier therefor.
 16. A method for combatting undesirable herbs which comprises contacting them with a herbicidally effective amount of a compound according to claim
 1. 17. A herbicidal composition comprising a herbicidally effective amount of a compound according to claim 4 and a carrier therefore.
 18. A method for combatting undesirable herbs which comprises contacting them with a herbicidally effective amount of a compound according to claim
 4. 19. A method for combatting undesirable herbs which comprises contacting them with a herbicidally effective amount of a compound according to claim
 3. 20. A method for combatting undesirable herbs which comprises contacting them with a herbicidally effective amount of a compound according to claim
 5. 